Cleaning method and cleaning apparatus

ABSTRACT

An object to be cleaned is cleaned with an cleaning agent which mixes a base cleaning agent such as silicon-containing cleaning agent or an isoparaffin containing cleaning agent with a surfactant or a hydrophilic solvent to promote the cleaning power. The object is rinsed with the base cleaning agent alone after it goes through the first cleaning step as described above. Then, this is followed by the finishing treatment by the use of hot air or steam drying. The base cleaning agents can be recovered and recycled, improving economy in the case with the use of two or more cleaning agents in combination. The excellent properties of degreasing and dewatering, comparable to those of flon system, can be obtained using a mixture of silicon-containing or isoparaffin-containing cleaning agents with surfactants and hydrophilic solvents and maintaining safety in environment.

This application is a divisional of application Ser. No. 08/177,697filed Jan. 4, 1994 still pending, which is a continuation of applicationSer. No. 07/768,554 filed Sep. 27, 1991 now abandoned, which is thenational phase of PCT/JP91/00359 filed Mar. 15, 1991.

BACKGROUND OF THE INVENTION

The present invention relates to a cleaning method and a cleaningapparatus using non-water system cleaning agents in place offlon-containing solvents such as flon 113, chlorine-containing solventsand lower alcohols.

DESCRIPTION OF THE RELATED ART

Flon-containing solvents such as flon 113 have been in general use as adewatering cleaning agent to dry metal parts, plated and coated parts,electronic parts, semiconductor parts and the like after they are washedwith water. Meanwhile, these flon-containing solvents and also suchorganic solvents as trichloroethane, trichloroethylene,tetrachloroethylene and carbon tetrachloride have been widely used as acleaning agent to remove oil stains and the like.

In recent years, however, it has been established that the discharge offlon leads to destruction of the ozone layer. Since flon 12 and flon 113have a high ozone destruction coefficient, there has been stagedreduction of their use the world over and it is expected that the flonswill be totally banned in the not too distant future.Chlorine-containing organic solvents such as trichloroethylene andtetrachloroethylene also are blamed for environmental problems such ascontamination of soils and underground waters and the restrains of theiruse have been more stringent with the elapse of time. Certain attemptsreflecting those circumstances have been made to develop substances offlon origin having the ozone destruction coefficient lower than that oftheir predecessors and, although some of them are in a stage ofindustrial production now, they are not regarded as a preferablecleaning agent because they do the ozone layer insignificant butpositive harm.

Under these circumstances, water system cleaning agents usingsurfactants or hydrophilic solvents which should not cause ecologicaldestruction or contamination have been thought better of to replacedegreasing cleaning agents containing organic solvents. These cleaningagents, however, have a drawback that they have the weak penetratingpower, incapable of completely cleaning up stains in narrow spaces ofthe parts or caked oil stains having a medium to high viscosity.

Meanwhile, many attempts have been made to probe the possibility ofdeveloping new cleaning agents by the use of a variety of surfactants toreplace organic solvent-containing dewatering cleaning agents but thedewatering effects as good as those of flon solvents have not beenobtained as yet. Further, when the abovementioned organicsolvent-containing cleaning agents are put to use for the dewateringcleaning purpose, their specific gravity is greater comparatively,resulting in the outcome that not only oils but also water rise to thesurface of the cleaning agent and are separated from the cleaning agentwhile they remain as they are contacted each other. Once they arecontacted in that way, the oils and waters are hard to separate. Sincethey should be discarded each independently, the disposal of wasteliquid is a difficult matter. Further, cleaning agents containingsurfactant are highly compatible with water, it is virtually impossibleto separate, repurify and recycle them.

On the other hand, a cleaning apparatus using conventional type cleaningagents usually comprises a mechanism solely controlling all of variousprocesses of immersing cleaning, vaporizing cleaning, showering cleaningand the like for the purpose of better cleaning efficiency and it ispre-conditioned that only one single cleaning agent but not others ispermitted to circulate in the system. This is because the recovery andrecycling of cleaning agent are hard to implement when two or more of itare used in combination. The system should be a stumbling block againstany attempts, for example to achieve by two or more cleaning agents thecleaning effects that would not be achieved by one of them alone.

Generally speaking, of the conventional type cleaning agents includingdewatering cleaning agents, those containing organic solvents such asflon have a drawback that they are blamed for ecological destruction.New cleaning agents investigated as a likely replacement of theseorganic solvent-containing agents have a drawback that the desiredsatisfactory effects are missing. On the other hand, the conventionalcleaning methods and systems have a drawback that recycling of cleaningagents and the disposal of removed waters and stain substance are a hardjob. Further, under these methods and systems, the use of two or morecleaning agents does not go along well with an attempt for efficientrepurification and recycling of them.

The present invention has been accomplished for the purpose of finding asolution to the above-mentioned problems incidental to the conventionaltype cleaning methods and cleaning apparatuses and the object of thepresent invention is to provide a new cleaning method and a new cleaningapparatus which make it possible to use more than one cleaning agents incombination and at the same time to recycle them. Another object of thepresent invention is to provide a new cleaning method and a new cleaningapparatus which make it possible to efficiently dispose of waters andstain substances that are removed from objects to be cleaned. Stillanother object of the present invention is to provide a new cleaningmethod and a new cleaning apparatus which should bring forth thecleaning power, water substitutability and the drying power which are asgood as those achieved when cleaned with flon-containing solvents.

SUMMARY OF THE INVENTION

The cleaning method of the present invention is characterized bycomprising the first cleaning step wherein an object to be cleaned iscleaned with a mixture of base cleaning agent with cleaning powerpromoting agent and the second cleaning step wherein the object iscleaned with the base cleaning agent alone after it goes through thefirst cleaning step.

Specific examples of cleaning agent for use in the first cleaning stepof the present invention include dewatering cleaning agent capable ofseparating waters and degreasing cleaning agent intended for use inremoving oil stains. Specific examples of base cleaning agent as usedherein include non-water system cleaning agent such assilicon-containing cleaning agent and isoparaffin-containing cleaningagent. But a variety of cleaning agents other than these can also beused herein as the need arises. Specific examples of cleaning powerpromoting agent include surfactant and hydrophilic solvent which provideor improve the cleaning or dewatering power in combination with thenon-water system cleaning agents. Further, the second cleaning step ofthe present invention fundamentally is a step of rinsing by the use ofthe base cleaning agent.

A silicon-containing cleaning agent enumerated as a non-water systemcleaning agent above is, for example a composition substantiallycomprising at least one low molecular weight polyorganosiloxane selectedfrom the group consisting of straight chain polydiorganosiloxanerepresented by the general formula: ##STR1## (wherein R is a hydrocarbongroup of single valence substituted by the same or different group orunsubstituted and 1 is an integer of from 0 to 5) and cyclicpolydiorganosiloxane represented by the general formula: ##STR2##(wherein R is a hydrocarbon group of single valence substituted by thesame or different group or unsubstituted and m is an integer of from 3to 7).

The above-mentioned low molecular weight polyorganosiloxane singlyexhibits the excellent penetrating or volatilizing power in narrowspaces of objects to be cleaned such as metal parts, electronic parts,semiconductor parts, coated parts and the like, providing therust-preventive properties, substituting waters well and vaporizing anddrying with a hot air at 60° C. or lower. Further, the straight chainpolydiorganosiloxane represented by the general formula (I) and thecyclic polydiorganosiloxane represented by the general formula (II) maybe used in combination.

R in the above-mentioned general formulae (I) and (II) is a substitutedor unsubstituted hydrocarbon group of single valence, including alkylgroup such as methyl group, ethyl group, propyl group and butyl group,unsubstituted hydrocarbon group of single valence such as phenyl groupand substituted hydrocarbon group of single valence such astrifluoromethyl group, but a methyl group is most preferable in order tokeep the system stable and volatility continuing for a certain period oftime. Of the above-mentioned low molecular weight polyorganosiloxane,those having the cyclic structure are preferable, andoctamethylcyclotrisiloxane, decamethylcyclopentasiloxane and mixturethereof are especially well suited.

By choosing the desired molecular structure of the above-mentioned lowmolecular weight polyorganosiloxane, its cleaning agent can be made tohave specific gravity Ddg satisfying the following formula (A) or (B):

    Wdg>Ddg                                                    (A)

    Wdg>Ddg>Odg                                                (B)

(wherein Ddg is specific gravity of the base cleaning agent, Wdg isspecific gravity of water and Odg is specific gravity of oil stains tobe cleaned.)

For example, when the Formula (B) is satisfied, water and oil stains canbe separated and repurification of cleaning agents and the disposal ofliquid wastes are carried out with ease.

As the above-mentioned isoparaffin-containing cleaning agent,compositions substantially comprising volatile isoparaffins having from1 to 30 carbon atoms can be mentioned and particularly isoparaffinschiefly comprising C₃ -C₁₅ cut are preferable from the viewpoint of thecleaning power. An isoparaffin containing cleaning agent usuallycomprises one or two or more of the above-mentioned volatileisoparaffins. These isoparaffins are volatile, harmless and odorless,achieving substantially as good effects as the above-mentioned lowmolecular weight polyorganosiloxane.

Further, silicon-containing and isoparaffin-containing cleaning agentswhich are mentioned as the base cleaning agent respectively are usedsingly but their mixture can also be used as a base cleaning agent. Forexample, a silicon-containing cleaning agent mixed with anisoparaffin-containing cleaning agent exhibits the effect of providing avery low freezing point, is well suited for use in cold areas andimproves the cleaning power as well.

As mentioned above, specific examples of cleaning power improving agentto be mixed with base cleaning agents include surfactant and hydrophilicsolvent. Surfactants are divided into cationic, anionic, nonionic,amphoteric and mixture types, depending upon their activating chemicalstructure. Every one of them can be used in connection with the presentinvention, contributing to the increase of the cleaning power.

Well suited for the present invention among these surfactants areanionic surfactants such as polyoxyalkylene alkylether sulfonate andphosphoric ester, nonionic surfactants such as polyhydroxy alcohol fattyacid ester, polyoxyalkylene fatty acid ester and polyoxyalkylenealkylether, amphoteric surfactants such as imidazoline derivative andcationic surfactants such as alkylamine salt and alkyl quaternaryammonium salt. Terpene compounds extracted from the natural sourceswhere their distribution as single substance is rare and higher fattyacid esters can also be mentioned. There are also mentioned thesynthetic compounds which are derived from the abovementioned compoundsby substituting a part of their chemical structure with a fluorine orsilicon atom.

As the hydrophilic solvent, those compatible with above-mentioned basecleaning agents and especially having the flash point of 40° C. orhigher are well suited for the practical use. Specific examples ofhydrophilic solvents include polyhydroxy alcohol and its derivativessuch as ethylene glycol monomethyl ether, ethylene glycol monoethylether, ethylene glycol monopropyl ether, ethylene glycol monobutylether, ethylene glycol monobutyl ether acetate and diethylene glycolmonobutyl ether, and of them diethylene glycol monobutyl ether isparticularly preferable on account of its compatibility with basecleaning agents and safety in the human. These compounds should have animproved volatility if in coexistence with low molecular weightpolyorganosiloxane and the like, and even water substitution and dryingstepes can be completed with their mixture alone. Further, loweralcohols such as ethyl alcohol or acetone or the like can be used incombination with base cleaning agents depending upon the latter's kindand uses. Further, a polyoxyalkylene alkylether represented by theformula: ##STR3## (wherein R is a hydrocarbon group of single valencehaving from 1 to 12 carbon atoms and n and p respectively are an integerof from 0 to 10, satisfying the formula n+p 1) is especially well suitedfor in the case where an isoparaffin-containing cleaning agent is usedas a base cleaning agent.

The above-mentioned base cleaning agents and cleaning power improvingagents are used in the following ways: fundamentally, a mixture of basecleaning agent with cleaning power improving agent is used in the firstcleaning step and a base cleaning agent alone in the second cleaningstep, but different ways are possible as well depending upon the use ofagents and the purpose of the subsequent step. Base cleaning agents andcleaning power promoting agents can be combined in various waysaccording to their use. For example, a mixture of base cleaning agentwith surfactant or hydrophilic solvent or a mixture of these three iswell suited as a degreasing cleaning agent. When anisoparaffin-containing cleaning agent is intended for use as the basecleaning agent, it may be put to use singly. It is acceptable as wellthat a mixture of silicon-containing and isoparaffin-containing cleaningagents is a base cleaning agent and this base cleaning agent further ismixed with one of above-mentioned cleaning power promoting agents. Asthe dewatering agent, a base cleaning agent can be used singly, butpreferably a surfactant or hydrophilic solvent is added to it.Especially the addition of a hydrophilic solvent is more preferable. Asthe rinsing cleaning agent, a base cleaning agent is used singly inprinciple, but the addition of a hydrophilic solvent is acceptable as sois the addition of a trace amount of a surfactant if required by thesubsequent stepes. Further, the base cleaning agent in the firstcleaning step need not be necessarily identical to its counterpart ofthe second step and for example it is quite probable that asilicon-containing cleaning agent is used as the base cleaning agent inthe first cleaning step and an isoparaffin-containing cleaning agent inthe second cleaning step.

Base cleaning agents and cleaning power promoting agents can be used invarious combinations as mentioned above and it is preferable to mix themwith due consideration given to solubility of each of them. For example,it is preferable to assort them in a way the resulting mixture has adifference of solubility parameter by 4 or less (hereinafter referred toas "SP value" for short). When two liquids having a large differencebetween their SP values must be mixed, still another liquid having amean SP value may be made to intervene as a mixing medium.

The mixing ratio of the above-mentioned surfactants is not particularlylimited but it is preferable to mix 50 parts by weight or less, or morepreferably, 20 parts by weight or less of them with 100 parts by weightof a base cleaning agent when the resulting mixture is intended for useas a degreasing cleaning agent. If the mixture should be used as adewatering cleaning agent, preferably 20 parts or less, or morepreferably, 3 parts by weight or less of a surfactant are mixed with 100parts by weight of a base cleaning agent. On the other hand, the mixingratio of hydrophilic solvents is not particularly limited as well, butit is preferable to mix 50000 parts by weight or less, more preferably10000 parts by weight or less of them with 100 parts of a base cleaningagent, when the resulting mixture is intended for use as a degreasingcleaning agent. If as a dewatering cleaning agent, preferably 100 partsby weight or less, more preferably 50 parts by weight or less of ahydrophilic solvent are mixed with 100 parts by weight of a basecleaning agent.

In the cleaning method of the present invention, the above-mentionedcleaning stepes are over with the drying treatment thereafter. In thisdrying treatment, the sufficient drying effects can be obtained with ahot air of comparatively low temperature such as 60° C. or lower. Saiddrying by means of the hot air can be replaced by that of steam with asteaming cleaning agent such as isopropyl alcohol (hereinafter referredto as "IPA" for short). Drying by steam gives a better finishing touchand is well suited for fine cleaning. The present invention may beapplied to metals, ceramics, plastics and the like; more specifically,metal parts, surface-treated parts, electronic and semiconductor parts,electric and precision machinery parts, optical parts, glass and ceramicparts and the like.

Incidentally, in the case where the cleaning method of the presentinvention is combined with steam cleaning (drying), the latter step canbe carried out immediately after the cleaning stepes withabove-mentioned dewatering or degreasing cleaning agents, dispensingwith rinsing cleaning of the base cleaning agent. In other words, anentire cleaning method may be made complete by comprising the step ofcleaning an object to be cleaned with a mixture of base cleaning agentand cleaning powder promoting agent and the step of steam drying theobject after it goes through the earlier cleaning processes. Again, ifcombined with steam cleaning, all cleaning operations may as well bedone with a base cleaning agent singly, depending upon stains to beeliminated. Mixtures of base cleaning agent with cleaning powerpromoting agent and how to use base cleaning agent have been discussedearlier.

The cleaning apparatus of the present invention will now be described indetail below:

The first cleaning apparatus of the present invention is characterizedby comprising first means for cleaning, for example with a mixture ofbase cleaning agent of non-water system with cleaning power promotingagent and second means for cleaning with the base cleaning agent alone.The second means for cleaning is followed by means for drying such ashot air drying or steam drying. Further, still another means is preparedto separate and recover the base cleaning agent alone from the mixtureof base cleaning agent and cleaning power promoting agent which isreclaimed from the above-mentioned first and second cleaning means andtherefore recovery and recycling of cleaning agents while two or more ofthem are permitted to circulate are feasible. The so recovered basecleaning agent is resupplied by recycling means to the first and secondmeans for cleaning.

The second cleaning apparatus wherein waters and oil stains are cleanedoff objects to be cleaned is characterized by comprising means forcleaning with a cleaning agent of non-water system having specificgravity smaller than that of waters but larger than that of oil stainsas mentioned above, means for removing waters which are incorporatedinto the cleaning agent and precipitated and separated in the lowermostpart thereof and means for removing oil stains which are incorporatedinto the cleaning agent and surfaced and separated at the uppermost partthereof. Non-water system cleaning agents to be used in these means havebeen described earlier and, because of the means for removing theprecipitated waters and another means for removing the surfaced oilstains, waters and oil stains separated from the objects to be cleanedcan be disposed of efficiently and each independently. Specific examplesof these cleaning steps include immersion vessel, spray vessel and thelike which may be operated in combination with ultrasonic wave,oscillation, mechanized stirring and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the construction of an cleaning apparatusused in an example of the present invention and

FIG. 2 is a diagram showing the construction of the other cleaningapparatus of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS(S)

The present invention will now be described with reference to thefollowing examples:

FIG. 1 is a diagram showing the construction of the cleaning apparatusused in one example of the present invention. Briefly, the cleaningapparatus shown herein is comprised of a process A for cleaning andwater substitution, a process B for rinsing and dewatering and amechanism C for recycling of cleaning agents. There are a first cleaningvessel 1 and a second cleaning vessel 2 each having the capability toconduct two types of separation by precipitation and overflowing and adewatering vessel 3 in the first process A for cleaning and watersubstitution.

In principle, the first vessel 1 and the second vessel 2 take care oftwo types of separation but either or both of them can be chosen,depending upon stains of the object to be cleaned. For example, eveneither separation by precipitation alone or separation by overflowingalone can function completely if so required by the object to becleaned. Further, each of the cleaning vessels in the process A may bedesigned to consist of one single vessel or a set of two or moredepending upon the required operating time and the quality standards togo by. The question of how many vessels there should be per set can finda solution in substantially the same way.

In this example, sets of 2 vessels each are used, and the first andsecond cleaning vessels 1 and 2 communicate with each other via thedrain line 2a and the overflow line 2b. These cleaning vessels areoperated in combination with ultrasonic wave, oscillation, mechanizedstirring, heating of cleaning agent, brushing process and the like inorder to increase the cleaning power, as need arises.

The above-mentioned first and second cleaning vessels 1 and 2respectively contain a dewatering cleaning agent D1 which mixes a basecleaning agent such as silicon-containing cleaning agent,isoparaffin-containing cleaning agent or mixture thereof with asurfactant. The cleaning agent D1 containing the surfactant ispre-designed to have specific gravity which is smaller than that ofwater but larger than that of oil stain and thus the waters Y separatedfrom the object to be cleaned are precipitated toward the lowermost partof the cleaning agent D₁ in the first and second cleaning vessels 1 and2. Meanwhile, the oil stains Z likewise separated rise to the surface ofthe same cleaning agent D₁ of the same cleaning vessels 1 and 2respectively.

The waters Y precipitated in the second cleaning vessel 2 are dischargedto the side of the first cleaning vessel 1 via the drain line 2a atregular intervals. Again, the waters Y precipitated in the firstcleaning vessel 1 are discharged at regular intervals into the cleaningagent recycling mechanism C which will be described later via the drainline 4. Meanwhile, the drain line 3a installed in the dewatering vessel3 is connected to the cleaning agent recycling mechanism C. The oilstains Z surfaced in the first and second cleaning vessels 1 and 2 areallowed to overflow gradually and go out of the cleaning system via theoverflow line 5 installed in the first cleaning vessel 1.

The dewatering cleaning agent D₁ in the first and second cleaningvessels 1 and 2 is extracted from the first cleaning vessel 1 by thecirculation line 6a, the filter 6 removes solids, water particles andinsoluble substances from the cleaning agent D₁ and then the cleaningagent D₁ returns to the second cleaning vessel 2. The cleaning agent D₁is thus purified at all times by its circulation via the filter 6,keeping the cleaning vessel 2 replete of the pure cleaning agent D₁though it is located at a downstream side of the cleaning process.

For example, humidity or water drops incorporated into the cleaningagent D_(l) can be eliminated with ease by means of above-mentionedfilter 6. Various types of filter can be chosen for the filter 6depending upon stains to be eliminated and/or liquids to be dewatered,but preferably it is a microporous filter of ceramic, glass, highmolecular weight organic substance or complex material thereof, having apore diameter of 0.1 to 20 μm.

In the second process B for rinsing and dewatering, there are a thirdcleaning vessel 7 and a showering-rinsing vessel 8. Below theshowering-rinsing vessel 8, there is a buffer tank 9 which isinterlinked with the third cleaning vessel 7 via the drain line 9a andthe overflow line 9b. This third cleaning vessel 7 is operated incombination with ultrasonic wave, oscillation, mechanized stirring,heating of cleaning agent, brushing process and the like as well, ifneed be.

The abovementioned third cleaning vessel 7 contains the cleaning agentD₂ compromising the base cleaning agent only which is same as used inabove-mentioned first process A. Specific examples mentioned ofnon-water system cleaning agent used in the above-mentioned firstprocess A are applied to the base cleaning agent used here. Thiscleaning agent D₂ is designed to have specific gravity smaller than thatof water but larger than that of oil stains. Thus, as in cleaningvessels in the first process A, the waters Y are precipitated andseparated in the lowermost part of the cleaning agent D₂, while the oilstains Z are surfaced and separated in the uppermost part thereof. Thewaters Y precipitated in the third cleaning vessel 7 are discharged tothe cleaning agent recycling mechanism C via the drain line 10 atregular intervals, while the oil stains Z surfaced in third cleaningvessel 7 are brought outside the cleaning system through the overflowline 11.

Further, the cleaning agent D₂ in third cleaning vessel 7 alwayscirculates via the filter 12, so that solids, water particles andinsoluble substances are eliminated from the cleaning agent D₂ by thefilter 12.

The recovery and recycling of cleaning agents in the cleaning systemwill now described below:

As mentioned earlier, the drain lines 4, 3a and 10 laid in the first,second and third cleaning vessels 1, 2 and 7 and the dewatering vessel 3are interlinked with the cleaning agent recycling mechanism Crespectively. The cleaning agent D₁ and D₂ in each vessel respectivelyis kept purified at all times by the filters 6 and 12 and when it isheavily soiled, the cleaning agent is subjected to fractionaldistillation in the cleaning agent recycling mechanism C after it issent there by the water pump 13 through the drain lines 4 and 10. Thecleaning agent D₁ collected in the dewatering vessel 3 is also sent tothe cleaning agent recycling mechanism C at regular intervals.

Brought into the cleaning agent recycling mechanism C, the soiledcleaning agent is fed to the filter 14 first to separate solids fromliquid, the solids are disposed of and the liquids alone are sent to thedistiller 15. The distiller 15 separates each ingredient of the cleaningagent, the waters and the oil stains using the difference of theirboiling point. The waters and the like left at distiller 15 are sent tothe decanter 16 for further separation. The waters and the like may beseparated and removed by a coalescer as preparatory step before they aresent to the distiller 15.

As used in the above-mentioned cleaning system, the dewatering cleaningagent D₁ is a mixture of the cleaning agent D₂ which is the basecleaning agent by itself with a surfactant and a repurified basecleaning agent or a repurified cleaning agent D2 can be obtained by theextraction of both soiled cleaning agents D₁ and D₂. Except for the sorepurified cleaning agent D₂, all extracted ingredients such assurfactant and water are discarded. The repurified cleaning agent D₂ isforwarded through the line 17 into the showering-rinsing vessel 8, thethird cleaning vessel 7 or the mixer 18 which is the supplier of thecleaning agent D₁ to the second cleaning vessel 2.

In the showering-rinsing vessel 8, showering cleaning is conducted onlywith the impurity-free cleaning agent D₂, with the supply ofabove-mentioned repurified cleaning agent D₂ or a completely newcleaning agent D₂ sent from the cleaning agent supply line 19. In themixer 18, the repurified or a brand new cleaning agent D₂ is mixed witha new surfactant supplied from the surfactant supply line 20 or ancleaning agent. previously combined with a high concentration ofsurfactant to produce a new batch of cleaning agent D₁. The so producedcleaning agent D₁ is supplied to the second cleaning vessel 2 as needarises.

An example of the cleaning procedures will now be described below withrespect to the cleaning system constructed as mentioned above:

When the object X to be cleaned is found carrying with it the waters Yand the oil stains Z, it is immersed at first in the order of the firstand second cleaning vessels 1 and 2 of the first process A in order toremove the oil stains Z and substitute the waters Y with the dewateringcleaning agent. Then, the cleaning agent D₁ is removed from the surfaceof the object X over the dewatering vessel 13.

The object X then is brought into the second process B, goes through thethird cleaning vessel 7 where it gets rid of the surfactant remaining onits surface and simultaneously is dewatered, arriving at theshowering-rinsing vessel 8 in order to finalize its surface purificationand dewatering by undergoing showering and rinsing with theimpurity-free cleaning agent D₂ alone.

This is followed by the drying treatment by a hot air dryer which is notillustrated herein to complete all of the cleaning processes.Incidentally, the hot air drying may be replaced by steam drying(cleaning) with IPA and the like.

Now, the present inventors took note of the fact that steam cleaning canachieve excellent effects in this system if due consideration is givento the following points: namely, (1) the compatibility of a steamcleaning agent with a liquid carried forward from the earlier process,(2) evaporation latent heat of the steam cleaning agent and thedifference of the evaporation latent heat between the steam cleaningagent and the liquid carried forward from the earlier process and (3)the boiling point.

With reference to the point (1), they had the finding that a steamcleaning agent can be a particularly effective factor if its SP valuehas a difference of 4 or less with that of the liquid carried forwardfrom the earlier process, except for some instances where hydrogen bondof molecules and interaction of polar groups must be given furtherconsideration. Steam cleaning is to condense the steam cleaning agent toform dews on the surface of the object to be cleaned so that these dewsdissolve and wash away the liquids attached to the object. If there is aSP value difference of more than 4 between the steam cleaning agent andthe liquid carried forward from the earlier process, sufficientsubstitutability is not obtained. Preferably the difference of SP valueis 3 or less and more preferably 2 or less. With reference to the point(2), it is preferable to put to use a steam cleaning agent having anevaporation latent heat which is differed from that of the liquidcarried forward from the earlier process by 5 folds or less. When thedifference of evaporation latent heat is larger than 5 folds, oneevaporates much faster than another, leaving the liquid having a largerevaporation latent heat behind on the object to be cleaned and keepingit remain as a blotch and the like there. Preferably the difference ofevaporation latent heat is 3 folds or less and more preferably 2 foldsor less. Further, preferably a steam cleaning agent has as small anevaporation latent heat as possible even when the above-mentioneddifference is satisfied. Preferably, the value of evaporation latentheat is 200 cal/g or less, more preferably 100 cal/g or less and mostpreferably 50 cal/g or less. It is especially important to satisfy theabovementioned points (1) and (2) with respect to the system of thepresent invention.

Moreover, with respect to the point (3) above, the boiling point of asteam cleaning agent must be higher than the surface temperature of theobject to be cleaned when it is subjected to steam cleaning. Preferably,the boiling point is higher than the surface temperature of the objectby 20° C. or more, more preferably by 30° C. or more and most preferablyby 50° C. or more; provided, however, that the difference between theboiling point and the surface temperature of the object to be cleanedcan be regulated by manipulating the surface temperature of the objectand thus that the desired difference can also be obtained by loweringthe surface temperature of the object prior to the steam cleaningtreatment. Still better results can be obtained, if satisfying the point(3) as well.

Meanwhile, silicon-containing cleaning agents and isoparaffin-containingcleaning agents are used in the process for rinsing cleaning of thepresent invention. Silicon-containing cleaning agents have the SP valueof approximately 7 and evaporation latent heat of almost 35 cal/g, whileisoparaffin-containing cleaning agents have the SP value ofapproximately 6 to 8 and the evaporation latent heat of almost 50 to 90cal/g. Compared with these agents, the above-mentioned IPA (SP value=11,evaporation latent heat=161 cal/g and boiling point=82° C.) is foundsatisfying all of the points (1) to (3) and evidently well suited as asteam cleaning agent after the cleaning process of the presentinvention.

Fundamentally, steam cleaning agents to be used in the present inventionpreferably satisfy the abovementioned points (1) and (2) and morepreferably the point (3) as well. Even whatever substances other thanIPA as described above may be used as a steam cleaning agent of thepresent invention, if they satisfy all of these 3 conditions. Forexample, a perfluoro compound represented by the general formula: C_(n)F_(2n+2)

(wherein n is an integer of from 4 to 12); and a perfluoro compoundrepresented by the structural formula: ##STR4## (wherein q and s are anyintegers) can be used therefor. These perfluoro compounds have the SPvalue of 5 to 6, the evaporation latent heat of almost 20 cal/g and theboiling point ranging from 50° C. to 200° C., satisfying all of theabove-mentioned conditions (1) to (3). A perfluoro compound having theboiling point of 50° C. to 150° C. is preferable for practical use incleaning. Further, perfluoro compounds do not exhibit compatibility withalmost all organic solvents and have not found their place as a steamcleaning agent in the past except for in the case with the removal ofparticles. In the present invention, silicon-containing cleaning agentsand isoparaffin-containing cleaning agents are used to rinse, and theperfluoro compounds have the compatibility with them (the SP valuedifference of 4 or less), capable of serving as a steam cleaning agentherein.

Steam cleaning agents such as IPA and perfluoro compound are notnecessarily used singly but, for example their mixture is acceptable aswell as their composition with the addition of silicon-containingcleaning agent, isoparaffin-containing cleaning agent or other organicsolvents such as acetone. Further, flon or chlorine-containing solventsare not necessarily ineligible as the organic solvent for use in amixture with IPA or perfluoro compound. It is desirable to stay awayfrom their use from the viewpoint of environmental contamination but itdoes not seem entirely unlikely that even flons or chlorines can findtheir usefulness at any time while they are subject to halfway step bystep restraints but are far away from the total ban. When a mixture isused as a steam cleaning agent, it is preferable that each component ofthe mixture should have the SP value and the evaporation latent heatsatisfying the abovementioned conditions (1) and (2). The values of eachsuch component should meet those mentioned as the example above. It alsois acceptable that an organic solvent having a mean value for SP andevaporation latent heat is interposed as a mixing medium.

Meanwhile, a very useful, one liquid for all type composition, a liquidwhich is good all the way from degreasing cleaning to drying, can beobtained by mixing abovementioned perfluoro compounds withsilicon-containing cleaning agents and/or isoparaffin-containingcleaning agents and also organic solvents such as IPA, ethanol, methanolacetone and dioxane. For the purpose of such one liquid for all typecomposition, it is preferable to mix 0.01 to 1000 parts by weight ofsilicon-containing cleaning agents and/or isoparaffin-containingcleaning agents and 0.01 to 1000 parts by weight of other organicsolvents with 100 parts by weight of an abovementioned perfluorocompound. The more preferable range of the mixing ratio with theperfluoro is 0.1 to 100 parts by weight of other components. This oneliquid for all type composition exhibits the properties of degreasing,dewatering and steam cleaning without the need for work-oriented changesof the composition and is good for all including operations fromdegreasing cleaning to drying.

So far, the above cleaning system has been described with chief emphasisplaced on dewatering cleaning but it can also be applied to degreasingcleaning if using the different kind of cleaning agents.

In the abovementioned cleaning system, drying is completed with blowingof a hot air at approximately 50 to 60° C. for approximately 5 minutes.Under the conventional methods wherein washing with hot water isfollowed by hot air drying, the drying time is almost as long as 15minutes even at the temperature as high as 120° C. to 150° C. On theother hand, in the present invention, the object to be cleaned is notexposed to a high temperature and can be forwarded to a next process asit is after hot air drying, does not require the space and time forcooling and contributes to the improvement of productivity to a greatextend. Not only the time required for drying is made shorter, but alsosince dewatering operation is conducted for every batch of the objectsto be cleaned, the finished products are free of irregularities indewatering and have the much improved quality, as far as the batch theybelong to is concerned. There also is no possibility of faulty finishedproducts with cracks which are attributable to irregularities incleaning and the level of product quality can be brought up very high.

In the cleaning system constructed as abovementioned, the cleaningagents have specific gravity smaller than that of waters but lager thanthat of oil stains, so a layer of cleaning agent intervenes betweenthose of waters and oil stains, separating waters from oils completelyand enabling the cleaning system to discard them efficiently and eachindependently. Their separation complete, waters and oils arerespectively disposed of by means of cleaning agents, but it is likelythat a trace amount of cleaning agents are incorporated into thediscarded waters and oils. The cleaning agents incorporated into oilsare consumed when the waste oils are incinerated. There is no problem inconnection with cleaning agents incorporated into waters as well,because they are separated from waters with ease by means of filter ordistiller.

With the cleaning system of such construction as described above, notonly the cleaning agents can be used efficiently and effectively, butalso the use of two or more cleaning agents in combination is madepossible. The amount of use of cleaning agents is reduced to a largeextent as two or more of them are put to use simultaneously,contributing much to a sharp cut of operating costs. The cleaningapparatus of the present invention may be allowed to operate aspreparatory step for steam drying with IPA, preventing waters from beingmixed with repurified IPA. Because of a large difference of boilingpoints existent between IPA and the above-mentioned dewatering cleaningagent as used in the present invention, it is made possible to implementsteam drying with IPA alone. Incidentally, waste waters once mixed withIPA have been regarded as hard to remove because their boiling point isclose to that of IPA, and they are often blamed for watermarks.

The present invention will now be described with reference to the otherexample. FIG. 2 is a diagram showing the construction of a cleaningapparatus used in the other example. Generally speaking, the cleaningapparatus as shown in the diagram is comprised of a cleaning process D,a rinsing process E, a drying process F and a cleaning agent recyclingmechanism G. There are a first cleaning vessel 21, a second cleaningvessel 22 and a dewatering vessel 23 in the first cleaning process D.Each cleaning vessel in the cleaning process D may be pre-designed toconsist of one single vessel or a set of two or more, depending upon therequired operating time and the quality standard to go by and thequestion how many vessels there should be per set finds a solution insubstantially the same way. The first and second cleaning vessels 21 and22 are operated in combination with ultrasonic wave, oscillation,mechanized stirring, heating of cleaning agent, brushing process and thelike in order to promote the cleaning power, if need be.

The above-mentioned first and second cleaning vessels 21 and 22respectively contain the degreasing cleaning agent D₃ which comprises abase cleaning agent such as silicon-containing cleaning agent,isoparaffin-containing cleaning agent or mixture thereof and ahydrophilic solvent. The cleaning agent D₃ containing the hydrophilicsolvent dissolves the oil stains of the object to be cleaned with thecleaning power provided by the hydrophilic solvent. In the case wherestains attached to the object to be cleaned are not completely dissolvedand removed in the first cleaning vessel 21 alone, they may be takenover by the second cleaning vessel 22 continuingly.

The cleaning agent D₃, either contained respectively in the first andsecond cleaning vessels 21 and 22 or brought into the dewatering vessel23, are forwarded to the cleaning agent recycling mechanism C via thedrain lines 21a, 22a and 23a. The filters 24 and 25 are respectivelyconnected to the first and second cleaning vessels 21 and 22, removingsolids and insoluble substances from the cleaning agent D₃ and thenreturning it to each cleaning vessel. Various types of filter may bechosen for the filters 24 and 25, depending upon what stains to becleaned up, but preferably they are a microporous filter having a poresize of 0.1 to 20 μm, made of ceramic, glass, high molecule organicmaterial or complex material thereof.

In the second rinsing process E, there are a third cleaning vessel 26and a showering-rinsing vessel 27. The third cleaning vessel 26 containsthe cleaning agent D₄ comprising only the same base cleaning agent as itis used in the first process D described above. Below theshowering-rinsing vessel 27, there is a buffer tank 28, while thisbutter tank 28 and the third cleaning vessel 26 are respectivelyinterlinked to the cleaning agent recycling mechanism C via drain lines28a and 26a. This third cleaning vessel 26 also is operated incombination with ultrasonic wave, oscillation, mechanized stirring,heating of cleaning agent, brushing process and the like if need be. Thecleaning agent D₄ contained in the third cleaning vessel 26 alwayscontinue circulating through the filter 29 which removes solids,insoluble substances and the like from the cleaning agent D₁.

In the third drying process F, there is a steam cleaning (drying) vessel30. This steam cleaning vessel 30 contains the steam cleaning agent 31which is a liquid of, for example IPA, perfluoro compound or mixturethereof as above described and the steam cleaning agent 31 is heated bythe heater 32, transforming into the steam 33. Inside the steam cleaningvessel 30, the steam 33 is condensed to form dews on the surface of theobject X to be cleaned and the cleaning agent D4 carried forward fromthe rinsing process E is dissolved into the so liquidized steam cleaningagent 31 and washed away. The object X to be cleaned is detained as longas necessary in the vicinity of the cooling chiller 34 located at theuppermost part to evaporate the steam cleaning agent 31 remaining on itssurface and thus complete the drying of the object X.

The cleaning agents in this cleaning system are recovered and recycledin substantially the same mechanism as in the example described earlier.

The cleaning by the use of above-mentioned cleaning system and theresult of its evaluation will now be described with reference to thespecific examples:

Examples 1 to 8

The examples of degreasing cleaning will be described first. A mixtureof 50 parts by weight of octamethylcyclotetrasiloxane (SP value=7) and50 parts by weight of diethylene glycol monobutylether (SP value=8) anda mixture of 50 parts by weight of volatile isoparaffin (SP value=7) and50 parts by weight of diethylene glycol monobutylether were prepared asthe cleaning agent in the first cleaning process. Anoctamethylcyclotetrasiloxane was used as the rinsing cleaning agent inthe second cleaning process. The various compounds listed in Table 1were used as the steam cleaning agent. The following charts shows the SPvalue, the evaporation latent heat and the boiling point of the steamcleaning agents listed in Table 1. The steam cleaning agents used inthese examples were selected with the SP value and the evaporationlatent heat of octamethylcyclotetrasiloxane as standard reference.

    ______________________________________                                                           Evaporation                                                                   Latent Heat                                                                              Boiling Point                                              SP Value                                                                              (cal/g)    (°C.)                                    ______________________________________                                        C.sub.8 F.sub.18                                                                           5         20         97                                           ##STR5##    6         20         102                                         IPA          11        161        82                                          Octamethylcyclo-                                                                           7         36         175                                         tetrasiloxane                                                                 Hexamethyldisiloxane                                                                       7         51         100                                         Acetone      10        62         56                                          Ethanol      13        204        78                                          ______________________________________                                    

Printed boards using the Sparkle Flux PO-F-4600, a brand ofrosin-containing flux (supplied by Senju Metal Industries Co., Ltd.: forchip-mounted board, SP value=approximately 10) were cleaned with thesecleaning agents. The ultrasonic wave cleaning was implemented at 45° C.for 3 minutes and then the rinsing cleaning for 2 minutes in the firstcleaning process. The so cleaned printed boards were subjected to steamdrying with each of the steam cleaning agents and the time span requiredfor drying was measured. Likewise, hot air drying at 50° C. wasconducted and the time span required for this type of drying wasmeasured. Further, after drying, the ion residue (μg NaCl/inch²) on thesurface of the printed boards was measured by an omegameter (NipponAlpha Metals Co., Ltd.) in accordance with the procedures provided forin MIL-P-55110C and MIL-P-28809A. Further, the flux residue was measuredwith the naked eye and microscopically, making an examination for thepresence of stains having the major axis of 0.05 mm or more. Thepractical usefulness was analyzed according to global judgement, markingexcellent as ⊚, good as ∘, fairly good as Δ and poor as x and theresults are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                        Steam cleaning composition (Parts by weight)                                         Octa-                                                                         methyl-                                                                            Hexa-         Dry-                                                                             Ion      Useful-             Cleaning               Other                                                                             cyclo-                                                                             methyl-       ing                                                                              reside                                                                            Appear-                                                                            ness                composition                                                                              Rinsing     organ-                                                                            tetra-                                                                             di-           time                                                                             (μg                                                                            ance (Global             (Parts by  composition ic sol-                                                                           silox-                                                                             silox-                                                                             Perfluoro                                                                              (sec-                                                                            NaCl/                                                                             (white                                                                             judge-              weight)    (Parts by wieght)                                                                      IPA                                                                              vents                                                                             ane  ane  compounds                                                                              ond)                                                                             In2)                                                                              reside)                                                                            ment)               __________________________________________________________________________    Example                                                                            Octa- Octamethylcyclo-                                                                       100                                                                              --  --   --   --        45                                                                               7  None ⊚                                                              7                   1    methyl-                                                                             tetrasiloxane                                                           cyclotetra-                                                                         100                                                                     siloxane                                                                      50                                                                       Example 2                                                                          Diethylene glycol monobutyl- ether 50                                                        0.5                                                                              --  1.5  --                                                                                  ##STR6##                                                                               19                                                                               6  None ⊚    Example                                                                            Volatile       -- Ace-                                                                              --   20   C.sub.8 F.sub.18                                                                        18                                                                               5  None ⊚    3    isoparaffin       tone          79                                            50                1                                                      Example  4                                                                         Diethylene glycol monobutyl- ether 50                                                        -- Ace- tone 3                                                                       --   30                                                                                  ##STR7##                                                                               17                                                                               8  None ⊚    Example             -- --  --   --   C.sub.8 F.sub.18                                                                        20                                                                               5  None ⊚                                                              3                   5                                    100                                      Example 6                                                                          Octa- methyl- cyclotetra- siloxane 50                                                        -- --  --   --                                                                                  ##STR8##                                                                               19                                                                               4  None ⊚                                                              3                   Example                                                                            Diethylene     -- --  --   --   --        35                                                                               8  None ⊚                                                              .                   7    glycol                                                                   Example                                                                            monobutyl-     (Dried by 50° C. warm wind)                                                                      125                                                                               6  None ◯       8    ether                                                                         50                                                                       Compar- ative example 1                                                            Octa- methyl- cyclotetra siloxane 50                                                IPA 100  -- --  --   --                                                                                  ##STR9##                                                                               58                                                                              18  A lot of dry                                                                       Xlots                    Diethylene                                                                    glycol                                                                        monobutyl-                                                                    ether                                                                         50                                                                       Compar- ative example 2                                                            Ethanol 100                                                                          ##STR10##                                                                             -- --  --   --                                                                                  ##STR11##                                                                              20                                                                              45  Present                                                                            X                   __________________________________________________________________________

As evident from Table 1, the sufficient degreasing cleaning power wasobtained and steam cleaning (drying) also resulted in a very goodoutcome in Examples 1 to 8. This is accounted for by the prearrangeddifference of SP value by 4 to 2 between the rinsing and steam cleaningagents. On the other hand, the agent having the SP value difference of 5or more in each of the Comparative Examples apparently failed to providethe sufficient cleaning powder.

Examples 9 to 12

Next, the examples of dewatering cleaning will be described. A mixtureof 99.5 parts by weight of octamethylcyclotetrasiloxane and 0.5 part byweight of polyoxyethylene oleyl ether (SP value=8) and a mixture of 99.0parts by weight of volatile isoparaffin (SP value=7) and 1.0 part byweight of sodium stearate were prepared as the dewatering cleaningagent. Further, various compounds listed in Table 2 were used as thesteam cleaning agent.

Miniature ball bearings made of stainless steel were subjected todewatering cleaning with these agents. 2 pieces of miniature ballbearings were immersed in water, then immersed in a dewatering cleaningagent at ordinary temperature for one minute (with oscillation) andsubjected to steam drying. Thereafter, the ball bearings were placed inthe predetermined amount of anhydrous ethanol, the remaining waters wereabsorbed thereto and the quantitative analysis with the waters wasconducted according to the Karl Fischer method. The rate of waterremoval was calculated according to the following formula:

The rate of water removal=(B-A)/B×100 (wherein A is the value (g) of thequantitative analysis according to the Karl Fischer method and B is thevalue (g) of the quantitative analysis after the blank test (excludingthe process in which the testing sample was thrown into water)).

Further, the post-drying appearance was evaluated according to thefollowing standard:

x: dried blobs visible with the naked eye.

∘: dried blobs invisible with the naked eye.

⊚: blob having the size of 50 μm or greater not observed by scanningelectron microscope.

These results are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                  Steam cleaning composition (Parts by weight)                                                                   Results of cleaning            Dewatering       Other                         Appearance                                                                           Rate                                                                               Useful-            composition      organic                                                                            Octamethylcyclo                                                                        Hexamethyl                                                                           Perfluoro                                                                              after  water                                                                              ness               (Parts by weight)                                                                           IPA                                                                              solvents                                                                           tetrasiloxane                                                                          disloxane                                                                            compounds                                                                              cleaning                                                                             removal                                                                            (*)                __________________________________________________________________________    Example                                                                            Octamethylcyclo                                                                        -- --   --       --     --       ⊚                                                                     99.3 .circleincircle                                                               .                  9    tetrasiloxanei                                                                99.5                                                                     Example                                                                            Diethylene                                                                             0.5                                                                              --   2.0      --     C.sub.8 F.sub.18                                                                       ⊚                                                                     99.3 .circleincircle                                                               .                  10   glycol                           97.5                                         monobutyl-                                                                    ether                                                                         0.5                                                                      Example 11                                                                         Volatile isoparaffin 99.0                                                              -- Acetone 0.5                                                                        2.0      --                                                                                    ##STR12##                                                                             ⊚                                                                     99.1 .circleincircle                                                               .                  Example                                                                            Sodium   -- --   --       --     C.sub.8 F.sub.18                                                                       ⊚                                                                     99.5 .circleincircle                                                               .                  12   stearate                         100                                          1.0                                                                      Compar-                                                                            Flon 113/                                                                              -- --   Flon 113/                                                                              --     --       ⊚                                                                     99.1 .circleincircle                                                               .                  tive surfactant       surfactant                                              Example                                                                            system           system                                                  3    100              100                                                     __________________________________________________________________________     *(Global judgement)                                                      

As evident from Table 2, the sufficient dewatering effect was obtainedin each of the Examples without the specific need for rinsing cleaning.

Examples 13 to 15

Next, the finishing cleaning (removal of particles) will be described.An octamethylcyclotetrasiloxane and a volatile isoparaffin were used asthe finishing cleaning agent. Further, various compounds listed in Table3 were used as the steam cleaning agent.

The cover glass for charge coupled device was subjected to finishingcleaning with these agents. The cover glass for CCD was cleaned with thefinishing cleaning agent at 45° C. in combination with the ultrasonicwave and then subjected to steam cleaning for the sake of finishingdrying. After drying, the appearance was analyzed and the amount ofdusts on the surface measured. The after drying appearance was analyzedin substantially the same way as in Example 9 above. The amount ofsurface dusts (0.5 μm or more) was measured by a particle checkerWM-1000 (Tokyo Optical Co., Ltd.) according to the laser method.

These results are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________                   Steam cleaning composition (Parts by weight)                                                                 Results of cleaning                               Other                                                                              Octamethyl-                                                                          Decamethyl-     Appearance                                                                           Amount of                Cleaning          organic                                                                            cyclotetra-                                                                          cycloki-                                                                             Perfluoro                                                                              after  remaining                                                                           Useful-            composition    IPA                                                                              solvents                                                                           siloxane                                                                             siloxane                                                                             compounds                                                                              cleaning                                                                             dusts                                                                               ness               __________________________________________________________________________                                                               *2                 Example                                                                             Octamethylcyclo                                                                        100                                                                              --   --     --     --       ⊚                                                                     15    .circleincircle                                                               .                  13    tetrasiloxane                                                                 100                                                                     Example        -- Acetone                                                                            3      --     *3       ⊚                                                                     12    .circleincircle                                                               .                  14                0.1                96.9                                     Example 15                                                                          Volatile isoparaffin 100                                                               -- --   --     --                                                                                    ##STR13##                                                                             ⊚                                                                     13    .circleincircle                                                               .                  Conpartive                                                                          Flon 113 -- Flon 113                                                                           --     --     100      ⊚                                                                     20    .circleincircle                                                               .                  Example                                                                             100         100                                                         Compar- tive Example 5                                                               ##STR14##                                                                             -- --   --     --                                                                                    ##STR15##                                                                             Δ A part of grinding                                                    materials remained                                                                   150   Δ            __________________________________________________________________________     *1 (/0.5 in2)                                                                 *2 (Global judgement)                                                         ##STR16##                                                                

As evident from Table 3, the sufficient particle control was foundachieve in each of the Examples.

Examples 16 to 19

As shown in Table 4, the certain degreasing cleaning agents wereprepared by mixing a volatile isoparaffin with various organic solvents.Further, a volatile isoparaffin was used as the rinsing cleaning agent.

Printed boards with flux were cleaned with these agents in accordancewith substantially the same procedures as in Example 1 and the result ofsubsequent hot air drying at 50° C. was analyzed in substantially thesame way as in Example 1. Further, a testing sample was prepared byapplying a spindle oil to a steel plate and baking the plate in afurnace at 150° C. for 48 hours. The oil baked on this testing samplewas subjected to cleaning (ultrasonic wave cleaning) and the time spanrequired for such cleaning was measured. The smaller the value is, thehigher the cleaning power is and these results are shown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________                                Flon 113/  Ion          Oil                                    Volatile  Other                                                                              ehtanol                                                                             Drying                                                                             residue                                                                             Appearance                                                                           cleaning                  Organic      isopa-    hydro-                                                                             azeotrope                                                                           time (μg NaCl/                                                                        (White time                      solvents     raffin                                                                             Kerosine                                                                           carbons                                                                            system                                                                              (second)                                                                           in2)  residue)                                                                             (second)                  __________________________________________________________________________    Example                                                                             Ethyl  98   --   --   --       40                                                                              11    ⊚                                                                     92                        16    alcohol 2                                                               Example                                                                             Diethylene                                                                           50   --   --   --       180                                                                              9    ⊚                                                                     60                        17    glycol mono-                                                                  butylether 50                                                           Example                                                                             d-Limonene                                                                           60   --   --   --       120                                                                              7    ⊚                                                                     45                        18    30                                                                            Ethyl                                                                         alcohol 10                                                              Example                                                                             α-Pinene                                                                       60   --   --   --       130                                                                              5    ⊚                                                                     40                        19    30                                                                            IPA 10                                                                  Compara-                                                                            --     --   100  --   --       820                                                                             40    X      150                       tive                                                                          example 6                                                                     Compara-                                                                            --     --   --   Isopropyl                                                                          --    >2,000                                                                             42    X      166                       tive                   benzene                                                example 7              100                                                    Compara-                                                                            Ethyl  --   --   Deamyl-                                                                            --    >2,000                                                                             14    ◯                                                                        135                       tive  alcohol 2        benzene                                                example 8              98                                                     Compara-                                                                            Diethylene                                                                           --   --   n-Decane                                                                           --       630                                                                             15    X      162                       tive  glycol           70                                                     example 9                                                                           monobutyl-                                                                    ether 30                                                                Compara-                                                                            --     --   --   --   100      20                                                                              11    ⊚                                                                     60                        tive                                                                          example 10                                                                    __________________________________________________________________________

As evident from Table 4, hot air drying could be brought to completionwithin a short span of time in the case of cleaning with an agentcontaining the isoparaffin as the chief ingredient, followed by rinsingwith the volatile isoparaffin (Examples 16 to 19). The ion residue waslow as well, nor was the white residue observed. Further, these agentswere fast at the speed of degreasing cleaning, exhibiting the cleaningpower equal to or better than that of a flon 113/ethane azeotropesystem. On the other hand, when cleaning and rinsing were conducted withalkylbenzene such as isopropylbenzene and diamylbenzene and straightchain paraffin such as n-decane and kerosine, drying by hot air resultedin a poor outcome and could not be completed even in 30 minutes. Thus,there were a lot of ion residues and too much flux components (whiteresidue) to be swept away.

Example 20

In accordance with substantially the same procedures as in Example 13,the cover glass for CCD was subjected to finishing cleaning withvolatile isoparaffin used as the finishing cleaning agent and thecleaning and drying properties were evaluated in substantially the sameway as in Example 13. Drying was conducted with a hot air at 50° C. Theresults are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                               Solvents               Amount of                                              used in the                                                                              Appearance  remaining                                              waste-removal                                                                            after       dusts                                                  process    cleaning    (/0.5 in.sup.2)                                 ______________________________________                                        Example  Volatile     ⊚                                                                          100                                         20       inparaffin                                                           Compara- Kerosine     Slow drying,                                                                              720                                         tive                  incidence of                                            example 11            dry blots                                                                     X                                                       Compara- Isopropyl-   Drying      2,000                                       tive     benzene      incomplete                                              example 12            even in 30                                                                    minutes                                                                       X                                                       Compara- Diamylbenzene                                                                              X           2,600                                       tive                                                                          example 13                                                                    Compara- n-Decane     ◯                                                                             350                                         tive                                                                          example 14                                                                    Compara- Flon 113/    ⊚                                                                           90                                         tive     ethanol                                                              example 15                                                                             azeotrope                                                                     system                                                               ______________________________________                                    

As evident from Table 5, the volatile isoparaffin in terms of finishingcleaning achieved the sufficient cleaning power which is equal to orbetter than that of flon 113, without causing post-cleaning dried blobsor dusts. On the other hand, in each of the Comparative Examples, theagent had low dryness, with a high incidence of dried blobs, while alarge amount of dusts were found attached to object to be cleaned duringthe drying process.

Examples 21 to 24

The printed boards with flux on were cleaned by the degreasing, rinsingand steam cleaning agents listed in Table 6 in accordance withsubstantially the same procedures as in Example 1 and the cleaning anddrying properties were evaluated in substantially the same way as inExample 1. The degreasing and rinsing cleaning were done at 45° C. for 5minutes in combination with ultrasonic wave. The results are shown inTable 6.

                                      TABLE 6                                     __________________________________________________________________________    Cleaning process (composition, parts by weight)    Results of evaluation                                       Fron                 Ion                                                      113/              Dry-                                                                             resi-                                                    ethanol           ing                                                                              due Apear-              Volatile                      n- azeo-    Stream   time                                                                             (μg                                                                            ance                iso-      Organic                                                                             Kero-                                                                             Isopropyl                                                                          diamly-                                                                            Dec-                                                                             trope                                                                             Rinsing                                                                            Drying   (sec-                                                                            NaCl/                                                                             (white              paraffin  solvents                                                                            sine                                                                              benzene                                                                            benzene                                                                            ane                                                                              system                                                                            process                                                                            process  ond)                                                                             in.sup.2)                                                                         residue)            __________________________________________________________________________    Example                                                                            98   Ethanol                                                                             --  --   --   -- --  Volatile                                                                           C.sub.8 F.sub.18                                                                       20 9   None                21        2                          iso-                                                                          paraffin                                 Example                                                                            96   Ethanol                                                                             --  --   --   -- --  ↑                                                                            C.sub.6 F.sub.14                                                                       15 6   None                22        4                                                                   Example                                                                            70   Diethylene                                                                          --  --   --   -- --  ↑                                                                            N(C.sub.4 F.sub.9).sub.3                                                               17 7   None                23        glycol                                                                        monobutyl-                                                                    ether                                                                         30                                                                  Example 24                                                                         30   Diethylene glycol monobutyl- ether 70                                               --  --   --   -- --  ↑                                                                             ##STR17##                                                                             15 8   None                Compar-                                                                            --   50    50  --   --   -- --  Kerosine                                                                           IPA      60 21  None                ative                                                                         example                                                                       16                                                                            Compar-                                                                            --   70    --  30   --   -- --  Isopropyl                                                                          IPA      82 15  Dry                 ative                                bensene              blobs               example                                                   present             17                                                                            Compar-                                                                            --   20    --  --   80   -- --  Diamyl-                                                                            IPA      98 31  Dry                 ative                                benzene              blobs               example                                                   present             18                                                                            Compar-                                                                            --   --    --  --   --   100                                                                              --  n-Decane                                                                           IPA      45 38  Dry                 ative                                                     blobs               example                                                   present             19                                                                            Compar-                                                                            --   --    --  --   --   -- 100 ←                                                                             ←   25 9   None                ative                                                                         example                                                                       20                                                                            __________________________________________________________________________

As evident from Table 6, when the printed boards were cleaned with anagent containing isoparaffin as the chief ingredient and a steamcleaning agent, drying was found completed within 15 to 20 seconds,accompanied by few ion residue and no remaining flux (white residue).These agents were found as effective as or more effective than a flon113/ethane azeotrope system.

Examples 25 to 27

Using the dewatering and steam cleaning agents listed in Table 7,miniature ball bearings were subjected to dewatering cleaning accordingto substantially the same procedures as in Example 9 and the cleaningand drying properties were evaluated in substantially the same way as inExample 9. The dewatering cleaning was implemented with the ballbearings immersed in the agents while stirring at 45° C. for one minute.The results are shown in Table 7.

                                      TABLE 7                                     __________________________________________________________________________    Cleaning process (composition of cleaning agent, parts by weight)                             Polyoxy-                             Result of                                                                     evaluation                               ethylene                                  Ratio               Volatile  Polyoxy-                                                                            butyl-             n- Flon113/                                                                            Steam         of water            iso-      ethylene                                                                            phenyl                                                                             Kero-                                                                             Isopropyl                                                                          Diamyl-                                                                            Dec-                                                                             surfactant                                                                          cleaning Appear-                                                                            removal             paraffin  oleylether                                                                          ether                                                                              sine                                                                              benzene                                                                            benzene                                                                            ane                                                                              system                                                                              process  ance %                   __________________________________________________________________________    Example                                                                            99.5 0.5   --   --  --   --   -- --    C.sub.6 F.sub.14                                                                       ⊚                                                                   99.3                25                                                                            Example                                                                            99.5 --    0.5  --  --   --   -- --    C.sub.8 F.sub.18                                                                       ⊚                                                                   99.4                26                                                                            Example                                                                            99.0 --    1.0  --  --   --   -- --    *3       ⊚                                                                   99.6                27                                                                            Compar-                                                                            --   --    --   100 --   --   -- --    C.sub.8 F.sub.18                                                                       Waters                                                                             62                  ative                                                remain-                  example                                              ing                      21                                                   X                        Compar-                                                                            --   0.5   --   --  99.5 --   -- --    C.sub.6 F.sub.14                                                                       X    91                  ative                                                                         example                                                                       22                                                                            Compar- ative example 23                                                           --   1.0   --   --  --   99.0 -- --                                                                                   ##STR18##                                                                             X    89                  Compar-                                                                            --   --    0.5  --  --   --   99.5                                                                             --    C.sub.8 F.sub.18                                                                       X    96                  ative                                                                         example                                                                       24                                                                            Compar-                                                                            --   --    --   --  --   --   -- 100   ←   ⊚                                                                   99.2                ative                                                                         example                                                                       25                                                                            __________________________________________________________________________     ##STR19##                                                                

Examples 28 to 29

Using the finishing and steam cleaning agents listed in Table 8, thecover glass for CCD was subjected to cleaning in accordance withsubstantially the same procedures as in Example 13 and the cleaning anddrying properties were evaluated in substantially the same way as inExample 13. The results are shown in Table 8.

                                      TABLE 8                                     __________________________________________________________________________    Waste                                   Amount of remain-                     removal process                                                                              Steam cleaning process                                                                          Appearance                                                                           ing dusts/in.sup.2                    __________________________________________________________________________    Example 28                                                                          Volatile isoparaffin                                                                    ##STR20##        ⊚                                                                      15                                   Example 29                                                                          Volatile isoparaffin                                                                    ##STR21##        ◯                                                                         18                                   Compar-                                                                             Kerosine F                 ◯                                                                        220                                   ative          C.sub.4 F.sub.9                                                example 26                                                                    Compar- ative example 27                                                            Isopropyl benzene                                                                       ##STR22##        ◯                                                                        340                                   Compar-                                                                             Diamylbenzene                                                                          C.sub.6 F.sub.14  ◯                                                                        250                                   ative                                                                         example 28                                                                    Compar- ative example 29                                                            n-Decane                                                                                ##STR23##        ◯                                                                        180                                   Compar-                                                                             Flon 113 ←            ⊚                                                                      32                                   ative (ethanol                                                                example 30                                                                          azeotrope system)                                                       __________________________________________________________________________

Example 30

A mixture of 50 parts by weight of hexamethyldisiloxane (SP value=7) and50 parts by weight of ethanol (SP value =13) was prepared as thecleaning agent in the first cleaning process and theoctamethylcyclotetrasiloxane was used as the rinsing cleaning agent inthe second cleaning process. Further, a C₈ F₁₈ was used as the steamcleaning agent. Using these agents, the cleaning and drying propertieswere evaluated in accordance with substantially the same procedures asin Example 1 and the results substantially as good as in Example 1 wereobtained.

In this Example, there was the SP value difference of more than 5between the cleaning agents or between hexamethyldisiloxane and ethanolbut because of the interaction between the polar groups, both thecompounds turned out compatible one another, resulting in theabove-mentioned favorable outcome.

Example 31

A one liquid for all type cleaning agent was prepared by mixing 100parts by weight of C₆ F₁₄ as a perfluoro compound, 25 parts by weight ofhexamethyldisiloxane as a silicon-containing cleaning agent and 3 partsby weight of acetone as an organic solvent. Meanwhile, the testingsample was prepared by applying to a steel plate YF33, a brand ofsilicon-containing press oil (supplied by Thoshiba Silicon Co., Ltd.)and baking the plate at 100° C. The testing sample was cleaned using theabove-mentioned one liquid for all type cleaning agent. Cleaning wasconducted at 40° C. for 3 minutes in combination with ultrasonic wave,followed by steam cleaning with the same agent.

In the infrared absorbing analysis with the so cleaned steel plate, apeak ascribed to silicon was not observed, resulting in the finding ofthe non-presence of silicon residues.

Industrial Applicability:

The excellent properties of degreasing cleaning, water substituting anddrying, comparable to those of conventional flon-containing cleaningagents, are obtained by the cleaning method of the present invention,unaccompanied by the possibility of environmental destruction andcontamination and, therefore, the cleaning method is useful as areplacement of the other one by the use of highly controversialflon-containing solvents. Further, under the present invention, thecleaning agents are recycled while two or more of them circulatesimultaneously and the waters and stains which are removed from objectsto be cleaned are disposed of efficiently, both contributing much to thesaving of materials relating to cleaning.

What is claimed is:
 1. A cleaning apparatus comprising:(a) firstcleaning means adapted for cleaning an object with a mixture containinga non-water system base cleaning agent and a cleaning power promotingagent, the first cleaning means comprising a plurality of cleaningvessels in sequence, wherein the cleaning vessels are connected witheach other such that said mixture is transmitted in sequence in thedirection opposite to that in which the object is transmitted, (b)second cleaning means adapted for cleaning the object with the basecleaning agent alone, the second cleaning means comprising a pluralityof cleaning vessels in sequence, wherein the cleaning vessels areconnected with each other such that said base cleaning agent istransmitted in sequence in the direction opposite to that in which theobject is transmitted, (c) distillation means for recovering a cleaningwaste liquid from at least one cleaning vessel selected from saidplurality of cleaning vessels, whereby said recovered waste cleaningliquid is distilled to recover said base cleaning agent alone, and (d)means for re-supplying said recovered base cleaning agent to at leastone cleaning vessel selected from said plurality of cleaning vessels. 2.A cleaning apparatus as claimed in claim 1, further comprising means forfiltering said cleaning waste liquid as a pretreatment for thedistillation.
 3. A cleaning apparatus as claimed in claim 1, comprisingmeans for transmitting said mixture and said base cleaning agent by atleast one mechanism selected from the group of an overflow mechanism anda drain mechanism.
 4. A cleaning apparatus as claimed in claim 1, whichcomprises a base cleaning agent which is at least one compound selectedfrom the group consisting of a silicon-containing cleaning agent and analiphatic hydrocarbon-containing cleaning agent.
 5. A cleaning apparatusas claimed in claim 4, wherein the base cleaning agent comprises saidsilicon-containing cleaning agent which is a polyorganosiloxane selectedfrom the group consisting of a straight chain polyorganosiloxanerepresented by the formula: ##STR24## and a cyclic polyorganosiloxanerepresented by the formula: ##STR25## wherein R¹ in each formula is asubstituted or unsubstituted hydrocarbon group, 1 is an integer from 0to 5, and m is an integer of from 3 to
 7. 6. A cleaning apparatus asclaimed in claim 4, wherein the base cleaning agent comprises saidaliphatic hydrocarbon-containing cleaning agent which is a volatileisoparaffine having from 6 to 15 carbon atoms.
 7. A cleaning apparatusas claimed in claim 1, further comprising means for drying the object.8. A cleaning apparatus as claimed in claim 7, wherein said means fordrying is conducted by use of heated air or in a heated oven.
 9. Acleaning apparatus as claimed in claim 7, wherein said means for dryingcomprise a vapor drying cleaning agent.
 10. A cleaning apparatus asclaimed in claim 9, wherein said vapor drying cleaning agent has adifference of solubility parameter of 4 or less and an evaporationlatent heat of 5 folds or less compared with the base cleaning agent.11. A cleaning apparatus as claimed in claim 9, wherein said vapordrying cleaning agent has a boiling point that is higher than thetemperature of the surface of the object to be cleaned by 20° C. ormore.